CN115586159A - Method for evaluating aging association degree of white spirit based on mid-infrared spectrum detection technology - Google Patents
Method for evaluating aging association degree of white spirit based on mid-infrared spectrum detection technology Download PDFInfo
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Abstract
The invention provides a white spirit aging association degree evaluation method based on a mid-infrared spectrum detection technology, realizes rapid detection of white spirit association degree, and belongs to the field of white spirit storage association degree detection, wherein the method comprises the following steps: preparing samples processed at different storage time and different temperatures; acquiring sample spectrum data through a Fourier infrared spectrum system; selecting the waveband of hydroxyl (4000 cm) ‑1 ～2600cm ‑1 ) (ii) a Normalization processing is carried out, and differences caused by different sampling amounts are eliminated; processing samples with different storage time through multimodal fitting, and grading the association degree; defining labels for all spectral data according to grading, and making a data set; preprocessing the spectral data in different modes; training and predicting are carried out through different models, effects of different combinations are compared, and reference is provided for realizing rapid detection of liquor association degree.
Description
Technical Field
The invention relates to a method for evaluating the aging association degree of white spirit based on a mid-infrared spectrum detection technology, and belongs to the technical field of quality detection special for wine storage.
Background
The traditional production and processing of the white spirit comprise raw material grinding, yeast preparation, fermentation, distillation, aging and blending, wherein the aging is a process of putting the white spirit into a container for storage, flavor development and irritation reduction. The aging degree of the white spirit is closely related to the storage time, the storage container, the temperature and the air circulation degree. In order to establish a standard and a healthy and controllable aging process, through years of research, 5 main mechanism theories of association, esterification, oxidation, dissolution and volatilization are summarized, and the main changes of the aging process of the white spirit are explained from the aspects of hydrogen bond association, internal reaction of the white spirit, external environment and a storage container. The hydrogen bond association of the white spirit is internal physical change which takes an ethanol-water association system as a main body, can form a stable cluster, and has important effects on improving the taste of the white spirit and reducing the irritation. Research shows that the association and stabilization period of the ethanol-water solution is far shorter than the required storage time of the white spirit, and the stable association clusters in the white spirit are damaged under the influence of internal component change and external environment in the aging process, so that the association-damage-re-association process is formed. Therefore, in the white spirit storage process, if the association degree can be detected in real time, the external environment can be changed according to the internal change of the white spirit, the aging process is accelerated, the quality of the white spirit can be monitored, and leakage can be searched, so that the yield is increased, the quality is ensured, and the economic benefit of the white spirit industry is greatly improved.
Currently, the assessment of the degree of association is mainly applied to hydrophobic organic solutions and all assess the association grade by viscosity. For example, in patent No. CN102564899B, the degree of contribution of intermolecular association to the structure of supramolecular solution was quantitatively calculated by comparing the zero shear viscosity before and after disruption of intermolecular association in a hydrophobically associating polyacrylamide solution. In patent No. CN102967534B, the association degree of the water-soluble associative polymer tackifier in the porous medium is obtained by measuring the viscosity of the water-soluble hydrophobic associative polymer tackifier aqueous solution added with beta-cyclodextrin with different concentrations to establish a quantitative association degree comparison curve. Whereas ethanol-water solutions with small changes in viscosity are clearly unsuitable for these methods to assess the degree of association.
The infrared spectrum is also called infrared absorption spectrum, which is a characteristic absorption spectrum curve generated by absorption generated by resonance of infrared photons and the quantized energy level of molecular vibration and rotation. The infrared spectrum is obtained by the interaction of photons and molecules through electric dipole moment transition when the photons interact with the molecules, namely, the hydroxyl group which is a strong polar group can better obtain the structural characteristics of the hydroxyl group through the infrared spectrum. Therefore, the method is feasible for evaluating the association degree by detecting and obtaining the spectral information of the ethanol-water solution through a Fourier infrared spectrometer and extracting hydrogen bond structure information from the spectral information.
Disclosure of Invention
The invention provides a method for evaluating the aging association degree of white spirit based on a mid-infrared spectrum detection technology. The method comprises the steps of carrying out infrared spectrum detection on ethanol-water solutions with different storage times in the same environment, carrying out normalization treatment on obtained spectrum data to eliminate differences caused by different sampling amounts, and carrying out hydroxyl spectrum band (4000-2600 cm) -1 ) And (3) performing multimodal treatment, and dividing the spectral band of the hydroxyl into four wave crests of free hydroxyl, single-bridge hydroxyl, polyhydroxy and weak hydrogen bonds. And (4) calculating an association equilibrium constant K of each spectrum data according to the peak type parameters, and classifying the association degree of the solution according to the storage time of the sample. And then obtaining spectral data with different association degrees through heating or cooling treatment, grading by the same method, and integrating all data to establish a data set. Dividing a training set and a test set according to the proportion of 4.
In order to realize the aim, the specific technical scheme of the invention is as follows:
the method for evaluating the aging association degree of the white spirit based on the mid-infrared spectrum detection technology comprises the following steps:
(1) Collecting infrared spectra (4000 cm) of 60% ethanol-water (V/V) solution processed at different storage time and temperature by Fourier transform infrared spectrometer -1 ～400cm -1 ) Data;
(2) Selecting hydroxyl wave band (4000 cm) -1 ～2600cm -1 )；
(3) Analyzing data difference caused by different sampling modes and sampling amounts, and selecting capillary sampling and normalization processing;
(4) Quantifying the data characteristics by utilizing multimodal fitting, and calculating a corresponding association equilibrium constant K;
(5) Performing association classification according to the storage time of the sample to prepare a data set;
(6) And performing regression prediction on the original data and the preprocessed data.
The Fourier infrared Spectrum detection system consists of a Frontier Fourier transform infrared instrument and special computer software Spectrum; wherein, the Frontier Fourier transform infrared instrument collects infrared spectrum data by transmitting light rays through a KBr tablet with a solution, and the parameters of spectrum collection are as follows: resolution 4cm -1 Scan number 8, spectral range 4000cm -1 ～400cm -1 (ii) a The software Spectrum performs a preliminary processing of the spectral curve, correcting the baseline of the Spectrum using an interactive baseline correction, and then smoothing the noise using the Boxcar function with a smoothing factor of 50.
In a preferred embodiment of the present invention, the hydroxyl band is selected in step (2) to eliminate the influence of the remaining data.
As a better embodiment in the present application, the method of capillary sampling and normalization processing is selected by comparing the spectral curve differences of different sampling modes and different sampling amounts in step (3), so that the detection result of the sample can be repeated.
As a preferred embodiment of the present application, the step (4) of using multi-peak fitting to separate the whole hydroxyl peak into free hydroxyl, monobridge hydroxyl and poly-hydroxylHydroxyl and weak hydrogen bond four wave peaks, and free molecule M is calculated according to parameters of each peak free And the polymerized cluster M assoc And calculating an association equilibrium constant K by an equilibrium formula.
As a preferred embodiment of the present invention, in the step (5), the association is graded according to the association equilibrium constant K at different storage times to prepare a data set.
As a preferred embodiment in the present application, in step (6), the data set is preprocessed by normalization, mean centering, and the like, and the raw data set and the preprocessed data set are input into modeling methods such as a one-dimensional convolution network, partial least squares, random forest, and support vector machine to perform regression prediction.
The method is used for evaluating the association degree of the white spirit and realizing rapid detection
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a white spirit aging association degree evaluation method based on mid-infrared spectrum detection technology, which evaluates the association degree of a hydrophilic solution, namely ethanol-water solution for the first time. The characteristics of the infrared spectrum curve are quantified by multimodal fitting, so that the association degree can be presented in a standard manner, a new reference is provided for the quality evaluation of the white spirit, and a new direction is provided for the development of the white spirit aging technology.
In the technical field, the infrared spectrum detection technology and the multi-peak fitting processing mode are combined, the whole hydroxyl peak is divided into four peaks of free hydroxyl, single-bridge hydroxyl, polyhydroxy and weak hydrogen bond, the cluster structure in the water solution is analyzed from the angle of microscopic molecular groups, and the deep association degree evaluation is realized. According to the equilibrium formula, each spectral curve is quantified, and the association degree of the solution can be visually represented.
And thirdly, in data processing, the invention reduces the difference caused by different sampling amounts by adopting normalization processing and improves the repeatability. According to the change characteristics of the solution spectral curves with different storage times, parameters of four peaks are divided into an association part and a non-association part, so that the concentrations of free molecules and polymer clusters in the solution are calculated, and the association equilibrium constant K is further calculated. The method realizes the quantification of the spectral data characteristics according to the actual storage time and the theory of hydroxyl hydrogen bonds, and is very persuasive to judge the association degree.
And (IV) in the aspect of prediction, the method adopts various preprocessing methods and prediction models, adjusts parameters to obtain an optimal model result, and provides reference for realizing rapid detection of the association degree of the white spirit.
The invention provides a method for evaluating the association degree of white spirit from the microscopic angle of a hydrogen bond structure. The method can be used for detecting the white spirit and also can be used for association evaluation of other hydrophilic organic aqueous solutions, and provides a new technical guide for hydrogen bond detection.
Drawings
FIG. 1 is a schematic flow chart of a method for assessing aging association degree of white spirit based on mid-infrared spectrum detection technology in the present invention;
FIG. 2 is a general graph of an infrared spectrum curve;
FIG. 3a is an infrared spectrum curve of the same sample at different sampling amounts;
FIG. 3b is a graph of the normalized spectrum;
FIG. 4 is a graph of spectra for different sampling modes;
FIG. 5 spectral curves for different storage times;
FIG. 6 is a schematic diagram of hydrogen bond structure peak separation in an infrared spectrum;
FIG. 7 is a graph showing the change of peaks at different storage times;
FIG. 8a is a graph of normalized processing data;
FIG. 8b is a diagram of standard normal variable transformation processing data;
FIG. 8c is a graph of multivariate scatter correction processing data;
FIG. 8d is a graph of moving average filter processed data;
FIG. 8e is a graph of mean centering data;
FIG. 8f is a graph of vector normalization processed data;
FIG. 8g is a diagram of wavelet transform processing data;
fig. 8h first order difference processed data diagram.
Detailed Description
The following embodiments of the present invention are provided as examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure of the present invention. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the features in the following embodiments and examples may be combined with each other without conflict.
It should be noted that, in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments.
Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials, equipment and methods used in the invention are all the raw materials, equipment and methods which are commonly used in the field unless otherwise specified.
Example (b):
a white spirit aging association degree evaluation method based on a mid-infrared spectrum detection technology comprises the following steps:
1. ethanol-water solution sample preparation
Mixing anhydrous ethanol and high purity water (conductivity as low as 0.04 μ s/cm) to obtain 60% ethanol-water (V/V) solution, and placing in a sealed container to prevent ethanol volatilization. Storing for 2 days, 5 days, 30 days, 50 days and 100 days in normal temperature environment respectively, and avoiding violent vibration in the period. Heating and cooling treatment is carried out before part of samples are detected, and then association degree of the solution is changed. Collecting infrared spectrum by KBr tablet method, preparing KBr tablet before collection, grinding KBr crystal with spectrum purity, and placing the solution on KBr tablet by capillary or injector for facilitating spectrum collection.
2. Infrared spectroscopy acquisition and preliminary data processing
The transmission infrared spectrum of the sample was taken using a Frontier fourier transform infrared spectrometer under constant temperature conditions. Two pieces of magnetic iron with holes press KBr tablets loaded with solution in the middle of the holes, so that light can directly penetrate through the KBr tablets. The parameters for spectrum acquisition were: resolution 4cm -1 Scanning number of 8, spectral range 4000-400cm -1 。
The preliminary spectral curve processing was performed in software Spectrum, using interactive baseline correction to correct the baseline of the Spectrum, and then using the Boxcar function to smooth the noise by a smoothing factor of 50. The Boxcar averaging function eliminates high frequency noise and makes the collected information clearer. When weak signals are collected, the method can be used for adding vertical resolution, reducing noise, improving dynamic characteristics such as signal-to-noise ratio and the like and a spurious-free dynamic range, and vertical precision is improved by averaging data collected adjacently by using a digital signal processing function.
3. Eliminating the effect of different sampling quantities and selecting the sampling mode
And (3) dripping solutions with obvious quantity difference on the KBr tablets by using a capillary tube, and detecting to obtain infrared spectrum curves, wherein the difference is mainly reflected as the difference of absorbance. To eliminate the effect of absorbance on the calculation of the association values, normalization of the data was required, considering that only the spectroscopic data (4000-2600 cm) of the hydroxyl moiety was required for association assessment -1 ) This portion is extracted and normalized.
The infrared spectrum detection has three sampling modes: capillary sampling, syringe-invasive sampling, and syringe-drip sampling. The capillary tube can be automatically adsorbed when contacting the solution wine, and then one end of the capillary tube is placed on the KBr pressing sheet, so that the solution naturally slides down, and the influence of the treatment on the solution is minimum. The solution was aspirated with a 1ml syringe and a drop of the solution was placed on a KBr slide by means of a close-in and remote drop. Both methods using a syringe have a greater disruption of the solution's association than using a capillary, and therefore capillary sampling is chosen to maintain the original association of the solution.
4. Determination of degree of association from storage time
The storage time of the white spirit is an important index for judging the taste of the white spirit, and one important factor is association degree. And distinguishing the association degree of the ethanol-water solution spectrum curve according to the storage time, and obtaining the spectrum data with different association degrees through heating and cooling treatment. And (3) carrying out capillary sampling detection on the ethanol-water solution stored for 2 days, 5 days, 30 days, 50 days and 100 days, comparing the obtained spectral curves, and analyzing the characteristics in the association and non-association directions.
In the infrared spectrum, there are three types of hydroxyl groups under the action of hydrogen bonds: free hydroxyl (3650-3590 cm) -1 ) Single bridge hydroxyl (3550-3450 cm) -1 ) And polyhydroxy (3400-3200 cm) -1 ). Free hydroxyl refers to hydroxyl groups that do not form hydrogen bonds and represent the major component of the non-association. By singly-bridged hydroxyl groups are meant hydroxyl groups that form only one hydrogen bond per atom, which represents the major component of the association. Polyhydroxy refers to a hydroxyl group in which one atom forms two hydrogen bonds, and only a bicyclic structure in a stable cyclic cluster has one polyhydroxy group. The stretching vibration wave number of methyl and methylene is less than 3000cm -1 The spectral curves sampled using the syringe have significant bulges in the methyl and methylene regions. In the case where the state of association is destroyed and the degree of association is low, the area occupied by the intermediate part between the alkane and the hydroxyl group is large, and therefore this part is a weak hydrogen bond (H-O8230; H-C) connecting the hydroxyl group and the methyl group. When the association degree of the solution is low, stable clusters are few, methyl and methylene are easy to interact with surrounding hydroxyl groups to form unstable weak hydrogen bonds, and small clusters with polyhydroxy groups are also easy to form. For solutions that have been recently destroyed by external forces, methyl and methylene groups also vibrate violently, showing a prominent peak group in the spectral curve. Thus, the higher the spectrum of the associationThe narrower and more concentrated the profile of the peaks.
5. Multimodal fitting and association determination
Infrared spectrum curve (4000-2600 cm) -1 ) Four sub-peaks of single-bridge hydroxyl, free hydroxyl, polyhydroxy and weak hydrogen bond are divided, alkane part is not fitted, and peak area (S) is passed 1 、S 2 、S 3 And S 4 ) Peak value (y) 1 、y 2 、y 3 And y 4 ) Wave number (x) corresponding to peak value 1 、x 2 、x 3 And x 4 ) And half width height (dx) 1 、dx 2 、dx 3 And dx 4 ) Isoparametric free molecule concentration [ M free ]Is stably expressed. There are many ways in which a spectral curve can be fitted, and limitations must be made to the extent to which the association is stable. Determining the half-width height dx of the peak area of the single-bridged hydroxyl group with the maximum peak area 1 =260, weak hydrogen bonding peak near alkane moiety, limiting its half width height dx 4 =180, to achieve normalization of the multimodal fit. Thus, each infrared spectrum curve is quantified, and an association value according with the spectral characteristics is calculated.
The basis of research on hydrogen bond association is the cluster aggregation equation:
thus, the association equilibrium constant K is calculated as
Wherein n is the association number, namely the average molecular number of all clusters in the solution; k is an association equilibrium constant, and the subject is used for judging the association degree of the solution; m free And M assoc Respectively represent free molecules and polymeric clusters, [ M ] in solution free ]And [ M assoc ]The concentrations of free molecules and polymeric clusters, respectively.
Obtained according to molecular dynamics simulationThe cluster ratio of the ethanol-water solution of 60% (V/V) in the ideal state was calculated, and the total number of associations n =6.75 in the ideal state. Concentration of free molecules [ M free ]It can be obtained from the infrared spectrum by multimodal fitting at the total molar concentration C 0 Of 60% (V/V) ethanol-water solution of total molar concentration C 0 The concentration was 32.5mol/L. The spectrum obtained by multiple detections of the same sample has certain difference, and the fitted parameters also have difference. And calculation of the association value requires a reduction in this difference while increasing the difference. Free hydroxyl peak is used to determine the concentration of free molecules [ M free ]The analysis shows that the peak areas of the polyhydroxy group and the weak hydrogen bond are represented by the free direction, but represent the stability of the cluster in a stably associated system. Thus, the concentration of free molecules [ M free ]The peak area of free hydroxyl is taken as a main body, and the peak areas of polyhydroxy and weak hydrogen bonds are multiplied by the peak value y respectively and added into the main body. Since the peak value y is less than 1 and increases with increasing peak area, the difference caused by a small amount of peak area change is reduced, and the difference is also highlighted when the peak area difference is large. Thus, the concentration of free molecules [ M free ]The calculation formula of (2) is as follows:
and concentration of polymeric clusters [ M ] assoc ]The calculation formula is as follows:
wherein, C 0 In terms of total molar concentration, S1, S2, S3 and S4 are respectively the peak areas of four standard peaks of single-bridge hydroxyl, free hydroxyl, polyhydroxy and weak hydrogen bonds, y3 and y4 are respectively the peak values of polyhydroxy and weak hydrogen bonds, and n is the association number.
Referring to table 1, table 1 shows the parameters obtained by performing multimodal fitting on the ir spectra for different storage times and the association equilibrium constant K calculated.
TABLE 1 multimodal fitting parameters and associated equilibrium constant K for different storage times
The K values for the same storage times fluctuate over a certain interval, whereby all spectral curves are classified into five classes: 0 (K is less than 0.000002), 1 (K is more than or equal to 0.000002 and less than 0.000008), 2 (K is more than or equal to 0.000008 and less than 0.00002), 3 (K is more than or equal to 0.00002 and less than 0.00007) and 4 (K is more than or equal to 0.00007).
6. Constructing a detection model
After the abnormal sample data are eliminated, a data set which divides 114 sample data into 5 types is established, and a training set and a testing set are distributed according to the proportion of 4. All sample data were baseline corrected, smoothed, and normalized. The preprocessing is performed by using methods of normalization, standard normal variable transformation, multivariate scattering correction, moving average filtering, mean centering, vector normalization, wavelet transformation, first-order difference and second-order difference, and regression prediction is performed in modeling algorithms of one-dimensional convolutional network (1D CNN), partial Least Squares (PLS), random Forest (RF) and Support Vector Machine (SVM) together with raw data.
The 1D CNN uses 8 convolutional layers to extract features with a linear rectification unit (ReLU) as an activation function and Mean Squared Error (MSE) as a loss function of an output layer, and adds a maximum pooling layer behind each two convolutional layers to retain main features. And outputting an association predicted value by the last layer of depth layer, wherein the association predicted value tends to a true value more and more under the approximation of an MSE loss function.
Before modeling prediction by PLS, principal Component Analysis (PCA) is used for data dimension reduction, and the PLS prediction result is best after the dimension reduction is carried out to 25 dimensions. When the number of trees in the RF algorithm is set to 200, the optimal result is obtained. The SVM algorithm uses a linear kernel function (linear), a polynomial kernel function (poly), and a radial basis kernel function (rbf) for prediction, respectively.
Referring to table 2, table 2 shows the prediction results obtained by combining different preprocessing methods and modeling algorithms.
TABLE 2 prediction results (each grid of data is in turn training set accuracy, test set accuracy and prediction root mean square error RMSE)
According to the prediction result, the best result is predicted by a support vector machine model of a 'linear' kernel function after preprocessing of the moving average filtering, and the prediction precision of the other two kernel functions of the support vector is higher than that of other models, so that the moving average filtering is matched with the support vector machine to predict the association of the white spirit. The original data are directly predicted, and the 1D CNN model has the best prediction effect.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention should be included in the protection scope of the invention.
Claims (8)
1. A white spirit aging association degree evaluation method based on a mid-infrared spectrum detection technology comprises the following steps:
(1) Collecting infrared spectra (4000 cm) of 60% ethanol-water (V/V) solution processed at different storage time and temperature by Fourier transform infrared spectrometer -1 ～400cm -1 ) Data;
(2) Selecting hydroxyl wave band (4000 cm) -1 ～2600cm -1 )；
(3) Analyzing data difference caused by different sampling modes and sampling amounts, and selecting capillary sampling and normalization processing;
(4) Quantifying the data characteristics by utilizing multimodal fitting, and calculating a corresponding association equilibrium constant K;
(5) Performing association classification according to the storage time of the sample to prepare a data set;
(6) And performing regression prediction on the original data and the preprocessed data.
2. A white spirit aging association degree evaluation method based on mid-infrared spectrum detection technology as claimed in claim 1, characterized in that in step (1), the strength of association degree is judged by storing infrared spectrum data of ethanol-water solution for different time, and the solution is processed by heating or cooling to obtain spectrum data of different association degrees.
3. The method for assessing aging association degree of white spirit based on mid-infrared spectrum detection technology as claimed in claim 1, wherein in step (2), a hydroxyl band is selected for the infrared spectrum collected in step (1) to eliminate the influence of other data.
4. A white spirit aging association degree evaluation method based on mid-infrared spectrum detection technology as claimed in claim 1, characterized in that in step (3), capillary sampling and normalization processing methods are selected by comparing spectral curve differences of different sampling modes and different sampling amounts, so that detection results of samples can be repeated.
5. A white spirit aging association degree evaluation method based on mid-infrared spectrum detection technology as claimed in claim 1, characterized in that in step (4), the whole hydroxyl peak is divided into four standard peaks of free hydroxyl, single-bridged hydroxyl, polyhydroxy and weak hydrogen bond by multimodal fitting, and the free molecular concentration [ M ] is calculated according to the parameters of each peak free ]And concentration of polymeric clusters [ M ] assoc ]：
Wherein, C 0 And (3) taking the total molar concentration as the reference, wherein S1, S2, S3 and S4 are peak areas of four standard peaks of single-bridge hydroxyl, free hydroxyl, polyhydroxy and weak hydrogen bonds respectively, y3 and y4 are peak areas of polyhydroxy and weak hydrogen bonds respectively, n is an association number, and finally, an association equilibrium constant K is calculated through an equilibrium formula.
6. A liquor aging association degree evaluation method based on mid-infrared spectrum detection technology as claimed in claim 1, characterized in that in step (5), association grade division is performed and a data set is made according to association equilibrium constants K of different storage times.
7. A liquor aging and association degree evaluation method based on mid-infrared spectrum detection technology as claimed in claim 1, characterized in that in step (6), the data set is preprocessed by methods of standardization, mean centering, etc., and the original data set and the preprocessed data set are input into modeling methods of one-dimensional convolution network, partial least squares, random forest and support vector machine to perform regression prediction.
8. A liquor aging association degree assessment method based on mid-infrared spectrum detection technology according to any one of claims 1-7, characterized in that the method is used for association assessment and rapid detection in liquor aging process.
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